Catalyst ligands, catalytic metal complexes and processes using and methods of making same

ABSTRACT

A new ligands that include a benzene ring in the backbone can be combined with a metal or metal precursor compound or formed into a metal-ligand complex catalyze a number of different chemical transformations, including olefin polymerization reactions. The ligands, complexes formed with the ligands and compositions including the ligands are useful catalysts, depending on the reaction.

FIELD OF THE INVENTION

[0001] The present invention relates to new organic compounds (e.g.,ligands), their metal complexes and compositions using those compounds;the invention also relates to the field of catalysis. In particular,this invention relates to new compounds which when combined withsuitable metals or metal precursor compounds provide useful catalystsfor various bond-forming reactions, including polymerizations and smallmolecule transformations. The invention also relates to combinatorialchemistry in that combinatorial techniques were used in connection withcreating the ligands and testing compositions containing the ligands.

BACKGROUND OF THE INVENTION

[0002] Ancillary (or spectator) ligand-metal coordination complexes(e.g., organometallic complexes) and compositions are useful ascatalysts, additives, stoichiometric reagents, monomers, solid stateprecursors, therapeutic reagents and drugs. Ancillary ligand-metalcoordination complexes of this type can be prepared by combining anancillary ligand with a suitable metal compound or metal precursor in asuitable solvent at a suitable temperature. The ancillary ligandcontains functional groups that bind to the metal center(s), remainassociated with the metal center(s), and therefore provide anopportunity to modify the steric, electronic and chemical properties ofthe active metal center(s) of the complex.

[0003] Certain known ancillary ligand-metal complexes and compositionsare catalysts for reactions such as oxidation, reduction, hydrogenation,hydrosilylation, hydrocyanation, hydroformylation, polymerization,carbonylation, isomerization, metathesis, carbon-hydrogen activation,carbon-halogen activation, cross-coupling, Friedel-Crafts acylation andalkylation, hydration, dimerization, trimerization, oligomerization,Diels-Alder reactions and other transformations. See, e.g., U.S. Pat.Nos. 5,576,460 and 5,550,236, both of which are incorporated herein byreference.

[0004] One example of the use of these types of ancillary ligand-metalcomplexes and compositions is in the field of polymerization catalysis.In connection with single site catalysis, the ancillary ligand offersopportunities to modify the electronic and/or steric environmentsurrounding an active metal center. This allows the ancillary ligand tocreate possibly different polymers. Ancillary ligands and ancillarymetal complexes that are similar to those disclosed herein have beendiscussed in WO 98/30609, incorporated herein by reference for allpurposes. However, that application does not specifically disclose anyof the ligands, complexes or compositions disclosed herein and does notdisclose any method of making the ligands (i.e., the ancillary ligands)of this invention.

[0005] It is always a desire to discover new ancillary ligands, whichupon coordination to a metal center or addition of a metal compound orprecursor will catalyze or assist in catalysis of reactions differentlyfrom known ligand systems. This invention provides new ancillary ligandsthat may be used for coordination to a metal center or included in acomposition with a metal or metal precursor compound. Upon coordinationto the metal center or inclusion in the composition, such ligandsinfluence the electronic and steric environment of the resultingcoordination complex and may catalyze reactions differently, includingmore efficiently and selectively than known systems.

SUMMARY OF THE INVENTION

[0006] In a first aspect, the invention disclosed herein is a new ligand(i.e., an ancillary ligand), which can be characterized by the generalformula:

[0007] wherein each R¹, R², R³, R⁴ and R⁶ is independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure and/or R¹ and R⁶ are joined together in a ring structure;and b is 0, 1, 2, 3 or 4. Where b is at least 2, two R⁶ groups may bejoined in a fused ring structure with the benzene ring in the backboneof the ligand. G is either oxygen or nitrogen. When G is oxygen, a is 0.When G is nitrogen, a is 1.

[0008] In a second aspect, this invention is a compound characterized bythe general formula:

[0009] wherein each R¹, R², R³, R⁴, R⁵ and R⁶ is independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino,thio, seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure and/or R⁴ and R⁵ are joined together in a ring structureand/or R¹ and R⁶ are joined together in a ring structure; G is eitheroxygen or nitrogen and a is either 1 or 2 depending on G; and b is 0, 1,2, 3 or 4. When G is nitrogen and a is 2, the two R³ groups may alsojoin to form a ring structure.

[0010] This invention also relates to a novel method of making these newligands. The general method of making these ligands is to start with acompound characterized by the general formula:

[0011] wherein R⁴ and R⁶ are as defined above and X is selected from thegroup consisting of chloro, bromo, iodo, triflate, tosylate andnonaflate; and R⁸ and R⁹ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof. This compound is reacted with an aminecharacterized by the general formula HNR¹R², where R¹ and R² are asdefined above. This provides ligands within the second aspect.Optionally, an acetyl or ketal functionality of the product is thenhydroylzed, providing ligands within the first aspect. Thereafter, theproduct can be reacted with a primary or secondary amine to transformthe ligand. Hydrogenation is thereafter an optional step. All steps mayor may not be performed using parallel or high throughput orcombinatorial methods.

[0012] In yet another aspect, this invention provides new metal-ligandcomplexes or compositions comprising the new ligands and a metalprecursor. For catalysis, the ligands can be included in a compositionincluding a suitable metal or metal precursor compound that can be ofthe form ML_(n), where the composition has catalytic properties. Also,the ligands can be coordinated with a metal precursor to formmetal-ligand complexes, which may be catalysts. Depending on the groupschosen for R¹, R² and R³ in the ligand (i.e., prior to reaction with themetal precursor), the metal-ligand complexes can be characterized by oneof many different general formulas depending on how the ligand attachesto or associates with the metal.

[0013] A further aspect of this invention provides for the novelligands, compositions or complexes to be created and tested in acombinatorial manner. Thus, the ligands, compositions or complexes maybe in an array with each ligand, composition or complex in a differentregion of a substrate. The number of ligands, compositions or complexeson a single substrate will vary according to the desired density, butwill typically have at least 10 ligands, compositions or complexes on asingle substrate.

[0014] These metal-ligand complexes or compositions catalyzepolymerization and copolymerization reactions, particularly withmonomers that are olefins, diolefms or otherwise acetylenicallyunsaturated. Other reactions that can be catalyzed include activation ofand/or formation of H—Si, H—H, H—N, H—O, H—P, H—S, C—H, C—C, C═C, C—C,C-halogen, C—N, C—O, C—S, C—P, and C—Si bonds. Specifically, suchreactions include carbonylation, hydroformylation, hydroxycarbonylation,hydrocarbonylation, hydroesterification, hydrogenation, transferhydrogenation, hydrosilylation, hydroboration, hydroamination,epoxidation, aziridation, reductive amination, C—H activation,insertion, C—H activation-insertion, C—H activation-substitution,C-halogen activation, C-halogen activation-substitution, C-halogenactivation-insertion, cyclopropanation, alkene metathesis, alkeneoligomerization, alkene polymerization, alkyne oligomerization, alkynepolymerization, CO-alkene co-oligomerization, CO-alkeneco-polymerization, CO-alkyne co-oligomerization and CO-alkyneco-polymerization.

[0015] Thus, in another aspect of the invention, a polymerizationprocess is disclosed for olefins, diolefins and other acetylenicallyunsaturated compounds. The polymerization process involves contactingmonomers to the catalyst compositions or to the coordination complexesof this invention under polymerization conditions. The catalystcompositions or the coordination complexes may be active catalyststhemselves or make be activated with a known activating technique orcompound. The polymerization process can be continuous, batch orsemi-batch and can be homogeneous or heterogeneous, as discussed furtherbelow.

[0016] Further aspects of this invention will be evident to those ofskill in the art upon review of this specification.

DETAILED DESCRIPTION OF THE INVENTION

[0017] The inventions disclosed herein are new ligands that may becombined with metals or metal precursor compounds to form coordinationcomplexes or compositions of matter, which are useful as catalysts forchemical reactions. The invention also is for processes for making theligand, processes for making the metal complexes and processes for usingthe resultant composition or coordination complex as a catalyst.Finally, the invention provides these new compounds and compositions andcomplexes in an array format.

[0018] As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R², R³, R⁴, and R⁵ can beidentical or different (e.g. R¹, R², R³, R⁴, and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). A named R group will generally have the structure thatis recognized in the art as corresponding to R groups having that name.For the purposes of illustration, representative R groups as enumeratedabove are defined herein. These definitions are intended to supplementand illustrate, not preclude, the definitions known to those of skill inthe art.

[0019] The term “alkyl” is used herein to refer to a branched orunbranched, saturated or unsaturated acyclic hydrocarbon radical.Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl,i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl), etc. In particular embodiments, alkyls have between 1and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20carbon atoms.

[0020] “Substituted alkyl” refers to an alkyl as just described in whichone or more hydrogen atom to any carbon of the alkyl is replaced byanother group such as a halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

[0021] The term “heteroalkyl” refers to an alkyl as described above inwhich one or more hydrogen atoms to any carbon of the alkyl is replacedby a heteroatom selected from the group consisting of N, O, P, B, S, Si,Se and Ge. The bond between the carbon atom and the heteroatom may besaturated or unsaturated. Thus, an alkyl substituted with aheterocycloalkyl, substituted heterocycloalkyl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, orseleno is within the scope of the term heteroalkyl. Suitableheteroalkyls include cyano, benzoyl, 2-pyridyl, ²-furyl and the like.

[0022] The term “cycloalkyl” is used herein to refer to a saturated orunsaturated cyclic non-aromatic hydrocarbon radical having a single ringor multiple condensed rings. Suitable cycloalkyl radicals include, forexample, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. Inparticular embodiments, cycloalkyls have between 3 and 200 carbon atoms,between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.

[0023] “Substituted cycloalkyl” refers to cycloalkyl as just describedincluding in which one or more hydrogen atom to any carbon of thecycloalkyl is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substituted cycloalkylradicals include, for example, 4-dimethylaminocyclohexyl,4,5-dibromocyclohept4-enyl, and the like.

[0024] The term “heterocycloalkyl” is used herein to refer to acycloalkyl radical as described, but in which one or more or all carbonatoms of the saturated or unsaturated cyclic radical are replaced by aheteroatom such as nitrogen, phosphorous, oxygen, sulfur, silicon,germanium, selenium, or boron. Suitable heterocycloalkyls include, forexample, piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl,piperidinyl, pyrrolidinyl, oxazolinyl and the like.

[0025] “Substituted heterocycloalkyl” refers to heterocycloalkyl as justdescribed including in which one or more hydrogen atom to any atom ofthe heterocycloalkyl is replaced by another group such as a halogen,alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substitutedheterocycloalkyl radicals include, for example, N-methylpiperazinyl,3-dimethylaminomorpholinyl and the like.

[0026] The term “aryl” is used herein to refer to an aromaticsubstituent which may be a single aromatic ring or multiple aromaticrings which are fused together, linked covalently, or linked to a commongroup such as a methylene or ethylene moiety. The common linking groupmay also be a carbonyl as in benzophenone or oxygen as in diphenyletheror nitrogen in diphenylamine. The aromatic ring(s) may include phenyl,naphthyl, biphenyl, diphenylether, diphenylamine and benzophenone amongothers. In particular embodiments, aryls have between 1 and 200 carbonatoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.

[0027] “Substituted aryl” refers to aryl as just described in which oneor more hydrogen atom to any carbon is replaced by one or morefunctional groups such as alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy,amino, thio and both saturated and unsaturated cyclic hydrocarbons whichare fused to the aromatic ring(s), linked covalently or linked to acommon group such as a methylene or ethylene moiety. The linking groupmay also be a carbonyl such as in cyclohexyl phenyl ketone.

[0028] The term “heteroaryl” as used herein refers to aromatic rings inwhich one or more carbon atoms of the aromatic ring(s) are replaced by aheteroatom(s) such as nitrogen, oxygen, boron, selenium, phosphorus,silicon or sulfur. Heteroaryl refers to structures that may be a singlearomatic ring, multiple aromatic ring(s), or one or more aromatic ringscoupled to one or more non-aromatic ring(s). In structures havingmultiple rings, the rings can be fused together, linked covalently, orlinked to a common group such as a methylene or ethylene moiety. Thecommon linking group may also be a carbonyl as in phenyl pyridyl ketone.As used herein, rings such as thiophene, pyridine, isoxazole,phthalimide, pyrazole, indole, furan, etc. or benzo-fused analogues ofthese rings are defined by the term “heteroaryl.”

[0029] “Substituted heteroaryl” refers to heteroaryl as just describedincluding in which one or more hydrogen atoms to any atom of theheteroaryl moiety is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio,seleno and combinations thereof. Suitable substituted heteroarylradicals include, for example, 4-N,N-dimethylaminopyridine.

[0030] The term “alkoxy” is used herein to refer to the —OZ¹ radical,where Z¹ is selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substitutedheterocycloalkyl, silyl groups and combinations thereof as describedherein. Suitable alkoxy radicals include, for example, methoxy, ethoxy,benzyloxy, t-butoxy, etc. A related term is “aryloxy” where Z¹ isselected from the group consisting of aryl, substituted aryl,heteroaryl, substituted heteroaryl, and combinations thereof. Examplesof suitable aryloxy radicals include phenoxy, substituted phenoxy,2-pyridinoxy, 8-quinalinoxy and the like.

[0031] As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical,where each of Z¹, Z², and Z³ is independently selected from the groupconsisting of alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

[0032] As used herein the term “boryl” refers to the —BZ¹Z² group, whereeach of Z¹ and Z² is independently selected from the group consisting ofalkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, amino, silyl and combinations thereof.

[0033] As used herein, the term “phosphino” refers to the group —PZ¹Z²,where each of Z¹ and Z² is independently selected from the groupconsisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, heteroaryl, silyl, alkoxy,aryloxy, amino and combinations thereof.

[0034] The term “amino” is used herein to refer to the group —NZ¹Z²,where each of Z¹ and Z² is independently selected from the groupconsisting of hydrogen; alkyl, substituted alky, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl and combinations thereof.

[0035] The term “thio” is used herein to refer to the group —SZ¹, whereZ¹ is selected from the group consisting of hydrogen; alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

[0036] The term “seleno” is used herein to refer to the group —SeZ¹,where Z¹ is selected from the group consisting of hydrogen; alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof

[0037] The term “saturated” refers to lack of double and triple bondsbetween atoms of a radical group such as ethyl, cyclohexyl,pyrrolidinyl, and the like.

[0038] The term “unsaturated” refers to the presence one or more doubleand triple bonds between atoms of a radical group such as vinyl,acetylenyl, oxazolinyl, cyclohexenyl, acetyl and the like.

[0039] The new ligands of this invention can be characterized by eitherof the general formulas:

[0040] wherein each R¹, R², R³, R⁴, R⁵ and R⁶ is independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino,thio, seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure and/or R⁴ and R⁵ are joined together in a ring structure;and b is 0, 1, 2, 3 or 4. G is an element selected from the groupconsisting of oxygen and nitrogen. In connection with structure I, a is0 when G is oxygen and a is 1 when G is nitrogen. In connection withstructure II, a is 1 when G is oxygen and a is 2 when G is nitrogen.Also in connection with structure II, when a is 2, the two R³ groups maybe the same or different and optionally may be joined together in a ringstructure.

[0041] In more specific embodiments, R¹ and R² are independentlyselected from a group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl and silyl. Specific examples of R¹ and R² are hydrogen,methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl,phenyl, naphthyl, benzyl, trimethylsilyl, and the like. In thoseembodiments where R¹ and R² are joined together in a ring structure, thering (including R¹, R² and N) has from 3 to 15 non-hydrogen atoms aspart of the backbone of the ring. Specific examples of R¹ and R²together are ethylene (giving a 3-member ring), propylene (giving a4-membered ring), butylene (giving a 5-membered ring), 3-oxopentylene(giving a 6-membered ring) and the like.

[0042] In a preferred embodiment, R¹ is a substituted or unsubstitutedphenyl and R² is hydrogen. If R¹ is a substituted phenyl, there may be1, 2, 3, 4 or 5 substituents attached to carbon atoms in the phenylring. Each of these substituents may be independently selected from thegroup consisting of alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinationsthereof. More preferably, there are 1, 2 or 3 substituents on thesubstituted phenyl and the substituents are selected from the groupconsisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl,cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.

[0043] More specifically, R³ is selected from a group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkyloxy, aryloxy, amino, silyl,boryl and phosphino. Specific examples of R³ are methyl, ethyl, propyl,butyl, cyclohexyl, cyclopropyl, cycloheptyl, t-butyl, phenyl, biphenyl,naphthyl, benzyl, pyridyl, furyl, quinolyl, morpholinyl, cyano, methoxy,ethoxy, t-butoxy, phenoxy, benzyloxy, dimethylamino, diethylamino,diphenylarnino, phenylmethylamino, benzylmethylamino, trimethylsilyl,dimethyl-t-butylsilyl, triphenylsilyl, triethoxysilyl, dimethylboryl,diphenylboryl, diphenoxyboryl, 1 ,2-dioxyphenylboryl,2,2′-biphenoxyboryl, 2,2′-dinaphthoxyboryl, diphenylphosphino,dibutylphosphino, dimethylphosphino, dicyclohexylphosphino,dicylcyclopentylphosphino, nitro, and methylphenylphosphino.

[0044] Most preferably, R³ is benzyl or a substituted or unsubstitutedphenyl. Where R³ is a substituted phenyl and there are 1, 2, 3, 4 or 5substituents on the phenyl ring, with each of said substituentsindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, hydroxy, halogens, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.Preferably in those embodiments there are 1, 2 or 3 substituents on thesubstituted phenyl and the substituents are selected from the groupconsisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl,cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof

[0045] Also in more specific embodiments, R⁴ is selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, heteroalkyl,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkyloxy, aryloxy, boryl, amino and silyl. In yet otherembodiments, R⁴may be selected from the group consisting of hydrogen,alkyl, aryl and cycloalkyl. Specific examples of R⁴ are hydrogen,methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl,phenyl, naphthyl, benzyl, pyridyl, furyl, morpholino, methoxy, ethoxy,butoxy, phenoxy, benzyloxy, dimethylboryl, diphenylboryl,methylphenylboryl, dimethylamino, diethylamino, diphenylamino,dibenzylamino, trimethylsilyl, triethoxysilyl, triphenylsilyl,triphenoxysilyl, dimethyl-t-butylsilyl, and the like.

[0046] In some embodiments where R³ and R⁴ are joined together in a ringstructure, the ring (including R³, R⁴, G and C) has from 4 to 15non-hydrogen atoms as part of the backbone of the ring. In connectionwith structure I, G is nitrogen and a is 1 and R³ is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino andcombinations thereof. Specific examples of R³ and R⁴ together areethylene (giving a 4-membered ring), butylene (giving a 6-memberedring), bicyclooctyl, bicyclohexyl, 2,2′-biphenyl (giving a dibenzo fused6-membered ring), 2,2′-binaphthyl (giving a dinaphtho fused 6-memberedring), 2,2′-biphenoxy (giving a 8-membered ring), 2,2′-dinaphthoxy(giving a 8-membered ring) and diethoxy (giving a 6-membered ring).

[0047] Also in more specific embodiments, R⁶ is selected from the groupconsisting of electron withdrawing and electron donating groups and b is0, 1, 2, 3 or 4. R⁶ can take any open position on the benzene ring thathelps form the backbone of the ligand. More specifically, R⁶ may bechosen from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, silyl, amino, alkoxy, aryloxy, phosphino, boryl, transitionmetals, halogens and combinations thereof. Specific examples of R⁶include methyl, ethyl, propyl, t-butyl, phenyl, cyano, acetyl, benzyl,nitro, dimethylamino, diethylamino, methylphenylamino,benzylmethylamino, trimethylsilyl, dimethylboryl, diphenylboryl,methylphenylboryl, dimethoxyboryl, chromium tricarbonyl, rutheniumtricarbonyl, and cyclopentadienyl iron. Optionally, two or more R⁵groups combine to form a fused ring structure with the aromatic groupthat forms a part of the ligand backbone. The additional fused ring mayor may not contain a heteroatom. Examples of the aromatic group that ispart of the backbone as combined with two or more R⁶ groups that haveformed a fused ring are naphthalene, quinoline, indole and the like.

[0048] In connection with structure II, R⁵ is present. R⁵ may beselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, aryl, substitutearyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino andsilyl. In more specific embodiments, R⁵ is selected from the groupconsisting of hydrogen, methyl, ethyl, propyl, butyl, cyclopentyl,cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, pyridyl, furyl,morpholino, methoxy, ethoxy, butoxy, phenoxy, benzyloxy, dimethylboryl,diphenylboryl, methylphenylboryl, dimethylamino, diethylamino,diphenylamino, dibenzylamino, trimethylsilyl, triethoxysilyl,triphenylsilyl, triphenoxysilyl, dimethyl-t-butylsilyl, and the like.Also in connection with structure II, R⁵ may be joined in a ringstructure with G and R³ in the backbone of the ring. Such a ring willhave at least four atoms in the backbone of the ring. In the case of aring, G can be oxygen or nitrogen and R³ forms a methylene bridge to R⁵.In this case, R⁵ is alkoxy, so that the ring has at least five atoms inthe backbone of the ring, as follows: C—O—(CH₂)_(x)—CH₂—O, with the lastO being bonded to the first C and x denoting the length of the alkylportion of R⁵. In yet other embodiments, R⁴ and R⁵ are joined in a ringstructure, having at least three atoms in the backbone. Where R⁴ and R⁵are joined together in a ring structure, the ring (including R⁴, R⁵ andC) has from 3 to 15 non-hydrogen atoms as part of the backbone of thering. Specific examples of R⁴ and R⁵ together are ethylene (giving a3-member ring), propylene (giving a 4-membered ring), butylene (giving a5-membered ring), 3-oxopentylene (giving a 6-membered ring) and thelike.

[0049] The ligands of this invention may be synthesized using an arylamination reaction. The synthesis can be carried out in solution phaseor solid phase (using organic or inorganic supports). For solid-phasesynthesis, the ligands may be left on the support and used with metaladded metal complexes as heterogeneous catalysts. Alternatively, theligands can be cleaved either before or after reaction with a metalprecursor and then used as a homogeneous catalyst. One the general routefor synthesis of the ligands of this invention is shown below in scheme1:

[0050] As shown in scheme 1, compounds 3 and 4 are within generalstructure I above, and compounds 2 and 5 are within general structure IIabove. Generally, the synthesis employs an aryl amination reaction toattach the nitrogen group to the benzene ring at the appropriatelocation. Following scheme 1, above, step 1 is an aryl aminationreaction starting with a compound characterized by the general formula:

[0051] wherein R⁴ and R⁶ are as defined above and X is selected from thegroup consisting of chloro, bromo, iodo, triflate, nonaflate, alkylsulfonates, aryl sulfonates and tosylate; and R⁸ and R⁹ areindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof. Compounds ofthis type can be purchased from Aldrich Chemical or prepared using knowntechniques. See, e.g., Greene, Theodra W. and Wuts, Peter G. M.,Protecting Groups in Organic Synthesis, 2^(nd) Edition (John Wiley &Sons, New York, N.Y. 1991).

[0052] The aryl amination reaction could also start with othercompounds, such as those characterized by the following general formulasin the following Schemes 2 and 3:

[0053] In these schemes, the variable groups have the previouslyindicated meanings.

[0054] Step 1 is any scheme is the aryl amination reaction. Thisreaction uses an amine that can be characterized by the general formulaHNR¹R², where R¹ and R² are as defined above. This aryl aminationreaction is typically performed using a catalyst that comprises known orpossibly new metal and ligand catalyst compositions. For example, thecatalyst may be characterized by the general formula M′/L′, where M′ isa complex that contains a metal selected from the group consisting oflate transition metals, preferably a Group 10 metal such as Pd, Ni orPt. M′ is any homogeneous or heterogeneous metal precursor catalyst orcatalyst, L′ is a ligand that may be selected from the group consistingof phosphine or nitrogen ligands. L′ may be monodentate, bidentate,tridentate, hemi-labile, unsubstituted or substituted, supported orunsupported, water-soluble or insoluble, soluble or insoluble in organicsolvents including fluorinated solvents. The reaction can take place atknown conditions, such as a temperature of from room temperature toabout 150° C. Aryl amination reactions are described in U.S. Pat. No.5,576,460 herein incorporated by reference.

[0055] Referring now to scheme 1, the second step of the reactionconverts compound 2 to compound 3 by hydrolysis of an acetal or ketalfunctionality. This reaction can be performed by one of skill in theart. See, e.g., Greene, Theodra W. and Wuts, Peter G. M., ProtectingGroups in Organic Synthesis, 2^(nd) Edition (John Wiley & Sons, NewYork, N.Y. 1991), herein incorporated by reference.

[0056] Thereafter in scheme 1, compound 3 can be reacted with a primaryor secondary amine for transform the ligand. The primary or secondaryamine in step 3 or 3′ can be characterized by the general formulaH_(3-a)NR³ _(a), where R³ is as defined above and a is 1 for a primaryamine and a is 2 for a secondary amine. A primary amine providescompound 4 in above scheme 1 following step 3. A secondary amine in thepresence of a hydride source provides a compound within above generalligand structure II in above scheme 1 following step 3′. If a primaryamine is employed, hydrogenation is thereafter an optional fourth stepin scheme 1.

[0057] Once the desired ligand is formed, it may be combined with ametal atom, ion, compound or other metal precursor compound. In manyapplications, the ligands of this invention will be combined with such ametal compound or precursor and the product of such combination is notdetermined, if a product forms. For example, the ligand may be added toa reaction vessel at the same time as the metal or metal precursorcompound along with the reactants. The metal precursor compounds may becharacterized by the general formula M(L)_(n) where M is a metalselected from the group consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10of the Periodic Table of Elements. In more specific embodiments, M isselected from the group consisting of Ti, Zr, Hf, V, Ta, Cr, W, Mo, Ru,Co, Ni, Pd, Fe, Mn, and Pt. L is a ligand chosen from the groupconsisting of halide, alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,hydroxy, boryl, silyl, hydrido, thio, seleno, phosphino, amino, andcombinations thereof. When L is a charged ligand, L is selected from thegroup consisting of hydrogen halogens, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, acetoxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof. When L is aneutral ligand, L is selected from the group consisting of carbonmonoxide, isocyanide, dibenzylideneacetone, nitrous oxide, PA₃, NA₃,OA₂, SA₂, SeA₂, and combinations thereof, wherein each A isindependently selected from a group consisting of alky, substitutedalkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.Specific examples of suitable metal precursor compounds include Pd(dba)₂(dba=dibenylideneacteone), Pd(OAc)₂ (Ac=acetate) and the like. In thiscontext, the ligand to metal precursor compound ratio is in the range ofabout 0.01:1 to about 100:1, more preferably in the range of about 0.5:1to about 20:1.

[0058] In other applications, the ligand will be mixed with a suitablemetal precursor compound prior to or simultaneous with allowing themixture to be contacted to the reactants. When the ligand is mixed withthe metal precursor compound, a metal-ligand complex may be formed,which may be a catalyst.

[0059] Depending on the substituents chosen for the ligand prior toreaction with the metal precursor compound, the metal complexes may becharacterized by any of the following general formulas. For generalligand structure 1, the possible metal complexes formed include:

[0060] For general ligand structure II, the possible metal complexesformed include:

[0061] In each of these formulas, each R¹, R², R³, R⁴, R⁵, R⁶, G, a andb are as defined above; and

[0062] M is a transition metal selected from the group consisting ofGroups 3, 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements.Selection of the metal is most preferably dependent on whether theligand is monoanionic or dianionic. In more specific embodiments, M isselected from the group consisting of V, Ta, Cr, W, Mo, Ru, Co, Ni, Pd,Fe, Mn and Pt.

[0063] L is independently each occurrence, a neutral and/or chargedligand. Generally, L is a ligand chosen from the group consisting ofhalide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, hydrido, thio, seleno, phosphino, amino, and combinationsthereof. When L is a charged ligand, L is selected from the groupconsisting of hydrogen, halogens, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof. When L is a neutral ligand, L isselected from the group consisting of carbon monoxide, isocyanide,nitrous oxide, PA₃, NA₃, OA₂, SA₂, SeA₂, and combinations thereof,wherein each A is independently selected from a group consisting ofalkyl, substituted alkyl, heteroalkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, and amino.

[0064] n is the number 0, 1, 2, 3, 4, and 5. Additionally, m is 1, 2, 3,or 4. M can be neutral, cationic or anionic. In this form, the ligandsof this invention that bind to a metal via the N atoms with dative bondsare shown with arrows and covalent binding is shown with a line.Coordination modes described above may or may not depend on the natureof ligands L on the metal M, and for a given ligand L, the coordinationmodes may switch from one to another at different stages of a catalyticcycle.

[0065] These transition metal-ligand complexes or metal/ligandcompositions of matter 30 catalyze reactions involving activation of andformation of bonds between H—Si, H—H, H—N, H—O, H—P, H—S, C—H, C—C, C═C,C═—C, C-halogen, C—N, C—O, C—S, C—P, and C—Si. Specifically, suchreactions include carbonylation, hydroformylation, hydroxycarbonylation,hydrocarbonylation, hydroesterification, hydrogenation, hydrosilylation,hydroboration, hydroamination, epoxidation, aziridation, reductiveamination, C—H activation, insertion, C—H activation-insertion, C—Hactivation-substitution, C-halogen activation, C-halogenactivation-substitution, C-halogen activation-insertion, alkenemetathesis, polymerization, alkene oligomerization, alkenepolymerization, alkyne oligomerization, alkyne polymerization,co-polymerization, CO-alkene co-oligomerization, CO-alkeneco-polymerization, CO-alkyne co-oligomerization and CO-alkyneco-polymerization. These reactions may occur at previously knownconditions (or possibly novel conditions). Moreover, these reactions maybe homogeneous or heterogeneous. In the case of heterogeneous reactions,the ligands may be supported, with or without the metal coordinated, onan organic or inorganic support. Suitable supports include silicas,aluminas, zeolites, polyethyleneglycols, polystyrenes, polyesters,polyamides, peptides and the like.

[0066] Polymerization catalysis with the compositions and metalcomplexes of this invention is a particularly effective process. Inparticular, the complexes and compositions of this invention are activecatalysts also for the polymerization of olefins, possibly incombination with an activator or activating technique. When an activatoror activating technique is used, those of skill in the art may usealumoxanes, strong Lewis acids, compatible noninterfering activators andcombinations of the foregoing. The foregoing activators have been taughtfor use with different metal complexes in the following references,which are hereby incorporated by reference in their entirety: U.S. Pat.Nos. 5,599,761, 5,616,664, 5,453,410, 5,153,157, 5,064,802, andEP-A-277,004. Preferred activators include methylalumoxane,trimethylaluminum, AgBF₄, AgBPh4, NaBAr′₄, H(OEt₂)₂BAr′₄ and the like(where Ar′ is a substituted aromatic, like perfluorophenyl or3,5-(CF₃)₂(C₆H₃)).

[0067] Ratios of neutral complex to activator are on the order of 1 to1000 to 1000 to 1. A scavenger can also be used with this invention.Scavengers useful herein include metal complexes, alumoxanes, aluminumalkyls and the like. Other additives that are standard forpolymerization reactions can be used.

[0068] The catalysts herein may be used to polymerize ethylenically oracetylenically unsaturated monomers having from 2 to 20 carbon atomseither alone or in combination. Monomers include C₂ to C₂₀ α-olefinssuch as ethylene, propylene, I -butene, I -hexene, 1-octene,4-mtheyl-1-pentene, styrene and mixtures thereof.

[0069] The compounds and catalysts of this invention usefully polymerizefunctionalized monomers, such as acetates and acrylates. Novel polymers,copolymers or interpolymers may be formed having unique physical and/ormelt flow properties. Such novel polymers can be employed alone or withother polymers in a blend to form products that may be molded, cast,extruded or spun. End uses for the polymers made with the catalysts ofthis invention include films for packaging, trash bags, foams, coatings,insulating devices and household items. Also, such finctionalizedpolymers are useful as solid supports for organometallic or chemicalsynthesis processes.

[0070] Polymerization can be carried out in the Ziegler-Natta orKaminsky-Sinn methodology, including temperatures of from 0° C. to 400°C. and pressures from atmospheric to 3000 atmospheres. Suspension,solution, slurry, gas phase or high-pressure polymerization processesmay be employed with the catalysts and compounds of this invention. Suchprocesses can be run in a batch or continuous mode. Examples of suchprocesses are well known in the art. A support for the catalyst may beemployed, which may be alumina, silica or a polymers support. Methodsfor the preparation of supported catalysts are known in the art. Slurry,suspension, solution and high-pressure processes use a suitable solventas known to those skilled in the art.

[0071] The ligands, metal complexes and compositions of this inventioncan be prepared and tested for catalytic activity in one or more of theabove reactions in a combinatorial fashion. Combinatorial chemistrygenerally involves the parallel or rapid serial synthesis and/orscreening or characterization of compounds and compositions of matter.U.S. Pat. No. 5,776,359 and WO 98/03521, both of which are incorporatedherein by reference generally disclose combinatorial methods. In thisregard, the ligands, complexes or compositions may be prepared and/ortested in rapid serial and/or parallel fashion, e.g., in an arrayformat. When prepared in an array format, for example, the ligands maybe take the form of an array comprising a plurality of compounds whereineach compound can be characterized by either of the general formulas:

[0072] wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino,thio, seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure; G is either oxygen or nitrogen. In connection withstructure I, a is 0 or 1 depending on G. In connection with structureII, a is 1 or 2 depending on G. Also, b is 0, 1, 2, 3 or 4.

[0073] In such a combinatorial array, typically each of the plurality ofcompounds has a different composition and each compound is at a selectedregion on a substrate such that each compound is isolated from the othercompounds. This isolation can take many forms, typically depending onthe substrate used. If a flat substrate is used, there may simply besufficient space between regions so that there cannot be interdiffusionbetween compounds. As another example, the substrate can be a microtiteror similar plate having wells so that each compound is in a regionseparated from other compounds in other regions by a physical barrier.

[0074] The array typically comprises at least 10 compounds, complexes orcompositions each having a different chemical formula, meaning thatthere must be at least one different atom or bond differentiating theplurality in the array. In other embodiments, there are at least 25compounds, complexes or compositions on or in the substrate each havinga different chemical formula. In still other embodiments, there are atleast 50 or 96 or 124 compounds, complexes or compositions on or in thesubstrate each having a different chemical formula. Because of themanner of forming combinatorial arrays, it may be that each compound,complex or composition is not pure. Typically, plurality of compoundsare at least 50% pure within said regions.

[0075] The catalytic performance (activity and selectivity) of theligands of this invention in combination with a suitable metal precursoror metal-ligand coordination complexes of this invention can be testedin a combinatorial or high throughput fashion. For any of the listedtransformation, thin layer chromatography (TLC) in combination withimaging technology may be employed. TLC is well known in the art, seefor example Vol. 1, Thin-Layer Chromatography, Reagents & DetectionMethods, Jork et al. (VCH Publishers, New York, N.Y. 1990).Polymerizations can also be performed in a combinatorial fashion, see,e.g., commonly owned provisional U.S. patent application Ser. No.60/096,603, filed Aug. 13, 1998 (having attorney docket no. 65304-010),herein incorporated by reference. High throughput screening can also beperformed optically and in parallel, for example, as disclosed incommonly owned U.S. patent applications Ser. No. 09/067,448, filed Apr.2, 1998, 08/947,085, filed Oct. 8, 1997, and 08/946,135, filed Oct. 7,1997, each of which is incorporated by reference.

EXAMPLES

[0076] General: All reactions were performed under argon atmosphere inoven-dried glass Schlenk tubes using standard Schlenk techniques. Allaryl halides, all amines, sodium t-butoxide,bis(dibenzylideneacetone)palladium, and all solvents used were purchasedfrom commercial sources and used as such. All solvents used were of theanhydrous, Sure-Seal® grade. Column chromatography was performed usingcommercially available Silica Gel 60 (particle size: 0.063-0.100 mm),hexanes and ethyl acetate. GCMS analyses were conducted on aHewlett-Packard 5890 instrument. ¹H, and ¹³C spectra were obtained usinga Bruker 300 MHz FT-NMR spectrometer. Chemical shifts in ¹H and ¹³C NMRspectra were calibrated with reference to the chemical shift of residualprotiated solvent. Elemental analyses were performed by E & RMicroanalytical Laboratory Inc., NJ. Ligand A was used for the arylamination reaction and is2-(2′-dicyclohexylphosphinophenyl)-2-methyl-1,3-dioxolane having thefollowing

[0077] structure: Ligand A Synthesis and use of ligand A is disclosed indetail in commonly owned and copending U.S. patent application Ser. No.09/062,128 filed Ap. 17, 1998 and incorporated herein by reference. AlsoU.S. provisional patent application Ser. No. ______, filed Aug. 6, 1998(Attorney Docket No. 98-22) and herein incorporated by referencediscloses other ligands that can be used in the aryl amination reaction.

[0078] The following ligands shown in structural form below are referredto using the code given below each structure:

[0079] Example 1: 2-Bromo-l(dimethoxymethyl)benzene (1a). To a 500 mLround bottom flask equipped with a reflux condenser were added2-bromobenzaldehyde (102. 5 g, 0.554 mol, Aldrich), trimethylorthoformate (64.9 mL, 0.594 mol, Aldrich), 10-camphor sulfonic acid(1.25 g, 5.40 mmol, Aldrich), and methanol (100 mL). The reaction washeated at reflux for 14 hrs and concentrated in vacuo. The residue wastaken up in 500 mL of ether, washed with 200 mL each of sat. aqueoussodium bicarbonate, water, and sat. aqueous NaCl, dryed over anhydroussodium sulfate, filtered and concentrated in vacuo. The crude productwas distilled through a 27 cm Vigrew column (b.p. 78-82 ° C./1.2 nmHg),affording a clear colorless oil (120.8 g, 94%). 1H-NMR (300 MHz, CDCl3)δ 3.37 (s, 6H), 5.54 (s, 1H), 7.18 (dt, 1H, J=1.7, 8.1 Hz), 7.31 (dt,1H, J=1.2, 7.5 Hz), 7.54 (dd, 1H, J=1.2, 8.1 Hz), 7.59 (dd, 1H, J=1.7,7.5 Hz). Mass spectrum (EI+) m/e 230, 232 (M+), 199, 201 (bp).

[0080] Example 2:2-[2′-(2,6-Dimethylanilino)phenyl]-2-methyl-1,3-dioxolane (2b-1): Amixture of 2-(2′-bromophenyl)-2-methyl- 1,3-dioxolane (362 mg, 1.49mmol), 2,6-dimethylaniline(189 mg, 1.56 mmol), NaO^(f)Bu (172 mg, 1.79mmol), Pd(dba)₂ (17 mg, 0.03 mmol), ligand A (21 mg, 0.06 mmol) intoluene (4 mL) was heated to 105° C. for 4.5 hours. The reaction wascooled to room temperature, taken up in diethyl ether (125 mL), washedwith water (2×30 mL) and brine (30 mL), dried over MgSO₄, filtered andconcentrated under vacuum. The crude product was purified by columnchromatography on silica gel using hexane (or hexanes: ethyl acetate) asthe eluent to afford compound 2b-1, after drying under vacuum, as anoff-white solid (yield: 391 mg, 93 %). ¹H NMR (CDCl₃): δ 7.41 (dd, 1H,J=7.8, 1.8 Hz, ArH), 7.13-6.99 (m, 4H, ArH), 6.70 (dt, 1H, J =7.5, 1.2Hz, ArH), 6.15 (dd, 1H, J=7.8, 0.9, ArH), 4.12 (m, 2H, O—CH—CH—O), 3.93(m, 2H, O—CH—CH—O), 2.18 (s, 6H, Ar—CH₃), 1.84 (s, 3H, CH₃). ¹³C NMR(CDC1₃): δ 143.5, 138.6, 135.2, 129.1, 128.5, 126.3, 125.6, 125.2,117.3, 112.6, 109.8, 64.1, 24.1, 20 18.3. Anal. for C₁₈H₂₁NO₂; Calcd: C,76.29; H, 7.47; N, 4.94; Found: C, 75.86; H, 7.46; N, 4.89.

[0081] Example 3:2-[2′(2-Chloro-6-methylanilinophenyl)]-2-methyl-1,3-dioxolane (2b-2): ACompound 2b-2 (381 mg, 96 % yield) was obtained as a colorless solidfrom the reaction of 2-(2′-bromophenyl)-2-methyl-1,3-dioxolane (318 mg,1.31 mmol), 2-chloro-6-methylaniline(195 mg, 1.38 mmol), NaO^(f)Bu (152mg, 1.58 mmol), Pd(dba)₂ (15 mg, 0.03 mmol), ligand A (18 mg, 0.05 mmol)in toluene (4 mL) at 105° C. for 2 hours. The experimental proceduredescribed for the synthesis of compound 2a-1 was generally followed. ¹HNMR (CDCl₃): δ 7.51 (m, 2H, ArH), 7.36 (d, 1H, J=7.9 Hz, ArH), 7.19 (d,1H, J=7.3 Hz, ArH), 7.13-7.06 (m, 2H, ArH), 6.83 (t, 1H, J=7.3 Hz, ArH),6.27 (d, 1H, J=7.9 Hz, ArH), 4.17 (m, 2H, O—CH—CH—O), 3.97 (m, 2H,O-CH-CH-O), 2.23 (s, 3H, Me), 1.89 (s, 3H, Me). ¹³CNMR (CDCl₃): δ 142.4,137.4, 136.8, 131.2, 129.3, 128.8, 127.5, 126.8, 126.4, 125.3, 118.5,113.5, 109.6, 64.1, 24.1, 18.8. Anal. for C₁₇H₁₈ClNO₂; Calcd: C, 67.21;H, 5.97; N, 4.61; Found: C, 66.92; H, 5.83; N, 4.53.

[0082] Example 4: 2-[2′(2-Isopropylanilinophenyl)]-1,3-dioxolane (2b-3):Compound 2b-3 (354 mg, 90% yield) was obtained as a yellow oil from thereaction of 2-(2′-bromophenyl)-1,3 -dioxolane (321 mg, 1.40 mmol),2-isopropylaniline (199 mg, 1.47 mmol), NaO^(f)Bu (141 mg, 1.47 mmol),Pd(dba)₂ (16 mg, 0.03 mmol), ligand A (27 mg, 0.08 mmol) in toluene (4mL) at 105° C. for 75 minutes. The experimental procedure described forthe synthesis of compound 2a-1 was generally followed. ¹H NMR (CDCl₃): δ7.45 (d, 1H, J=7.6 Hz, ArH), 7.33-7.12 (m, 4H, ArH), 7.05 (t, 1H, J=7.4Hz, ArH), 6.85 (t, 1H, J=7.4 Hz, ArH), 6.68 (br.s, 1H, NH), 5.93 (s, 1H,O—CH—O), 4.10 (m, 4H, O—CH₂—CH₂—O), 3.13 (septet, 1H, J=6.8 Hz, CHMe₂),1.26 (d, 6H, J=6.8 Hz, 2 Me′s). ¹³C NMR (CDCl₃): δ 143.8, 140.0, 139.5,129.7, 127.2, 126.3, 126.1, 123.7, 122.9, 121.6, 118.9, 115.5, 103.0,64.9, 27.8, 22.8. Anal. for C₁₈H₂₁NO₂; Calcd: C, 76.29; H, 7.47; N,4.94; Found: C, 75.75; H, 7.96; N, 4.81.

[0083] Example 5: 2-[(2′,4′,6′-trimethylphenyl)amino]benzaldehyde(3a-1). In an oven-dried 500 mL Schlenk flask were added sodiumt-butoxide (5.77 g, 60.0 mmol, Aldrich), Pd(dba)₂ ( 0.144 g, 0.250 mmol,ACROS), ligand A (0.174 g, 0.500 mmol) and 1a (14.45 g, 62.6 mmol).Toluene (130 mL, anhydrous, Aldrich) and 2,4,6-triethylaniline (8.71 g,64.4 mmol, Aldrich) were added and the reaction was heated to 105 C. for6 hrs. An additional 1.44 g of sodium t-butoxide was added to thereaction and the reaction was heated at the same temperature for anadditional 1 hr, at which time a GLC analysis revealed the reaction wascompleted. The reaction was cooled to room temperature. The reactionmixture was diluted with 100 mL of ether and washed with 200 mL each ofwater and sat. aqueous NaCl, dried over anhydrous sodium sulfate,filtered and concentrated in vacuo, affording 20.1 g of a red oil ascrude product. The crude material was chromatograghed through a 6×15 cmsilica gel column (1-5 % step gradient of ether in hexanes). During thisoperation, the acetal was partially hydrolyzed. The fractions containingthe acetal and the aldehyde were combined and concetrated in vacuo,affording 16.61 g of a yellow viscous oil. The oil was stirred in amixture of THF (50 mL), water (25 mL), and acetic acid (25 mL) at 22° C.for I hr. THF was removed by evaporation and 200 mL of ether was added.The organic phase was washed with 100 mL each of water and sat. aqueoussodium bicarbonate, dried over anhydrous sodium sulfate, filtered andconcentrated in vacuo, affording 14.47 g of a deep yellow viscous oil(97%). A GLC analysis and H-NMR analysis indicated this material waspure. ¹H NMR (CDCl₃, 300 MHz): 9.97 (s, 1H), 9.50 (s, 1H), 7.56 (d,J=7.8 Hz, 1H), 7.3-7.2 (m, 4H), 6.98 (s, 2H), 6.74 (t, J=7.5 Hz, 1H),6.24 (d, J=8.4 Hz, 1H), 2.34 (s, 3H), 2.16 (s, 6H) ppm. ¹³C NMR (CDCl₃,75 MHz): 194.3, 149.9, 136.5, 136.4, 136.3, 135.7, 133.6, 129.2, 118.3,115.7, 112.3, 20.9, 18.1 ppm.

[0084] Example 6: 2-[2′,6′-(diisopropylphenyl)amino]benzaldehyde (3a-2).In an oven-dryed 250 mL Schlenk flask were added sodium t-butoxide (2.88g, 30.0 mmol, Aldrich), Pd(dba)₂ (72 mg, 0.13 mmol, ACROS), ligand A (87mg, 0.25 mmol). Toluene (100 mL, anhydrous, Aldrich), 1 (5.70 g, 24.6mmol), and 2,6-diisopropylaniline (4.37 g, 24.6 mmol, Aldrich) wereadded and the reaction was heated to 105 C. for 14 hrs, at which time aGLC analysis revealed the reaction was completed. The reaction wascooled to room temperature. The reaction mixture was stirred with 50 mLof water and filtered to remove insoluble materials. The organic layerwas separated and washed with 50 mL of sat. aqueous NaCl, dried overanhydrous sodium sulfate, filtered and concentrated in vacuo, affording8.88 g of a red oil as crude product. The crude material was subjectedto hydrolysis in the similar way as 3a-1 ( THF (50 mL), water (25 mL),and acetic acid (25 mL) at 22 C. for 1 hr). The crude product waspurified by flash chromatography on a 7×20 cm silica gel column (2.5%ether in hexanes), affording 6.68 g of a very yellow viscous oil (96 %).IR (liquid film) 3292, 1660 cm⁻¹. ¹H—NMR (300 MHz, CDCl₃) δ 1.08 (d, 3H,J=6.9 Hz), 1.13 (d, 3H, J=6.9 Hz), 3.04 (sept, 2H, J=6.9 Hz), 6.20 (d,1H, J=8.5), 6.70 (t, 1H, J=7.4 Hz), 7.18-7.23 (m, 3H), 7.32 (t, 1H,J=7.6 Hz), 7.53 (dd, 1H, J=7.8, 1.5 Hz), 9.54 (br.s, 1H), 9.94 (s, 1H).¹³C—NMR (75 MHz, CDCl₃) δ 23.0, 24.5, 28.4, 112.5, 115.7, 118.0, 123.9,128.0, 133.4, 135.5, 136.1, 147.3, 151.0, 194.2. Mass spectrum (EI+) mle281 (M+), 266 (bp).

[0085] Example 7: This example is a general procedure for the formationof 2-mesitylaminobenzaldehyde imines: To a solution of2-mesitylaminobenzaldehyde 3a-1 (957 mg, 4 mmol) in dichloroethane (6mL) was added benzylamine (429 mg, 4 mmol) via syringe, followed by acatalytic amount of p-toluenesulfonic acid monohydrate (18 mg, ˜1%) and4Å molecular sieves. The reaction was heated to reflux overnight whilestirring under argon. The disappearance of the aldehyde and formation ofthe imine was followed by GC/MS. To the crude product was added aminopropyl silica and the mixture was shaken. The mixture was then filteredand the resulting solution was concentrated. The product was thenprecipitated with hexanes. The precipitate was washed with cold hexanesand dried in vacuo. 4a-1: ¹H NMR (CDCl₃, 300 MHz): 10.49 (s, 1H), 8.57(s, 1H), 7.4-7.25 (m, 6H), 7.12 (t, J=8 Hz, 1H) 7.01 (s, 1H), 6.69 (t,J=8 Hz, 1H), 6.26 (d, J=8 Hz, 1H), 4.69 (s, 2H), 2.32 (s, 3H), 2.13 (s,6H) ppm. ¹³C NMR (CDCl₃, 75 MHz): 165.3, 148.3, 139.8, 136.3, 135.5,135.2, 133.8, 131.2, 128.9, 128.4, 127.6, 126.8, 116.9, 115.1, 111.5,65.12, 20.9, 18.2 ppm. GC-MS: m/z 328 (M)⁺. 4a-2: ¹H NMR (CDCl₃, 300MHz): 10.7 (s, 1H), 8.74 (s, 1H), 7.48 (d, J=8 Hz, 1H), 7.33 (d, J=8 Hz,1H), 7.2 (m, 4H), 7.05 (s, 2H), 6.79 (t, J=8 Hz, 1H), 6.35 (d, J=8 Hz,1H), 3.01 (m, 6.9 Hz, 1H), 2.40 (s, 3H), 2.28 (s, 6H), 1.34 (d, J=6.9Hz, 6H) ppm. ¹³C NMR (CDCl₃, 75 MHz): 162.3, 148.5, 146.5, 136.3, 135.7,135.1, 134.5, 131.9, 129.0, 127.1, 120.9, 117.3, 115.4, 111.8, 33.7,24.1, 20.9, 18.3 ppm. GC-MS: m/z 356 (M)⁺.

[0086] Example 8: This example is a general procedure for the formationof 2-(2,6-diisopropylphenyl)aminobenzaldehyde imines. To a solution of2-[(2,6-diisopropylphenyl) amino]benzaldehyde 3a-2 (126 mg, 0.45 mmol)in dichloroethane (500 μL) was added 2,6-diisopropylaniline (84 μL, 0.45mmol) via syringe, followed by a catalytic amount ofp-toluenesulfonicacid monohydrate (10 mg, 10%). The resulting solution was concentratedand the resulting oil was heated overnight (external temperature 120 °C.). The disappearance of the aldehyde and formation of the imine wasfollowed by GC/MS. To the crude product was added dichloroethane (1 mL)followed by amino propyl silica and the mixture was shaken. The mixturewas then filtered and the resulting solution was concentrated. Theproduct was then precipitated with methanol. The precipitate was washedwith cold methanol and dried in vacuo. 4a-3: ¹H NMR (CDCl₃, 300 MHz):10.56 (s, 1H), 8.40 (s, 1H), 7.4-7.1 (m, 8H), 6.74 (t, J=7 Hz, 1H), 6.34(d, J=8 Hz, 1H), 3.25 (m, 2H), 3.14 (m, 2H), 1.3-1.1 (m, 24H) ppm. ¹³CNMR (CDCl₃, 75 MHz): 166.2, 150.4, 147.9, 138.6, 134.9, 134.8, 132.6,127.9, 124.8, 124.2, 123.5, 116.6, 115.5, 112.4 ppm. GC-MS: m/z440 (M)⁺.

[0087] Example 9: This example is a general procedure for the formationof 2-mesitylaminobenzaldehyde 2-aminomethylenes. To 4a-2 (0.17 mmol, 60mg) in dichloroethane (2 mL) was added acetic acid (60 μL) followed byNaBH(OAc)₃ (0.34 mmol, 70 mg). The resulting mixture was shaken at roomtemperature for 2 hours. The crude product was extracted from an aqueousNa₂CO₃ solution with dichloroethane (3×2 mL) then passed through a plugof silica gel and concentrated to afford a pale yellow oil. 5a-1: ¹H NMR(CDCl₃, 300 MHz): 7.27 (d, J=7.4 Hz, 1H), 7.3-7.1 (m, 3H), 6.97 (s, 2H),6.9-6.7 (m, 3H), 6.61 (s, 2H), 6.29 (d, J=8 Hz, 1H), 4.42 (s, 2H), 2.91(m, J=6.9 Hz, 1H), 2.36 (s, 3H), 2.19 (s, 6H), 1.30 (d, J=6.9 Hz, 6H)ppm. ¹³C NMR (CDCl₃, 75 MHz): 146.0, 145.8, 139.5, 135.8, 134.7, 134.6,130.0, 129.1, 128.9, 127.2, 122.8, 117.4, 114.2, 112.2, 48.2, 33.2,24.2, 20.6, 18.2 ppm. GC-MS: m/z 358 (M)⁺

[0088] It is to be understood that the above description is intended tobe illustrative and not restrictive. Many embodiments will be apparentto those of skill in the art upon reading the above description. Thescope of the invention should, therefore, be determined not withreference to the above description, but should instead be determinedwith reference to the appended claims, along with the full scope ofequivalents to which such claims are entitled. The disclosures of allarticles and references, including patent applications and publications,are incorporated herein by reference for all purposes.

What is claimed is:
 1. A compound characterized by the general formula:

wherein each R¹, R², R³, R⁴ and R⁶ is independently selecte( hydrogen,alkyl, substituted alkyl cycloalkyl, substituted cy heterocycloalkyl,substituted heterocycloalkyl, aryl, substit substituted heteroaryl,alkoxy, aryloxy, silyl, boryl, phosphi combinations thereof, optionally,R¹ and R² are joined toge R³ and R⁴ are joined together in a ringstructure and/or R¹ and R³ are joined in a ring structure; G is eitheroxygen or nitrogen and a is 0 or 1 depending on G; and bis 0, 1, 2, 3 or4.
 2. The compound of claim 1, wherein each of R¹ and R² isindependently selected from the group consisting of alkyl, substitutedalky, heteroalkyl, cycloalkyl, substituted cycloalkyl, aryl andsubstituted aryl.
 3. The compound of claim 2, wherein R¹ and R² arejoined in a ring, wherein the said ring has between 5 and 10non-hydrogen atoms.
 4. The compound of claim 3, wherein said ring hasbetween 5 and 6 non-hydrogen atoms in the backbone of the ring.
 5. Thecompound of claim 1, wherein R¹ is a substituted or unsubstitued phenyl.6. The compound of claim 5, wherein R¹ is a substituted phenyl and thereare from 1-5 substituents on said phenyl ring, with each of saidsubstituents independently selected from the group consisting of halide,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.7. The compound of claim 6, wherein there are 1, 2 or 3 substituents onsaid substituted phenyl and said substituents are selected from thegroup consisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl,butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 8. The compound of claim 1, whereinR⁴ is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloaLkyl, heteroalkyl, aryl, substitutearyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino andsilyl.
 9. The compound of claim 8, wherein R⁴ is selected from the groupconsisting of hydrogen, alkyl, aryl and cycloalkyl.
 10. The compound ofclaim 1, wherein R⁴ is joined in a ring structure with G and R³, whereinsaid ring has at least four atoms in the backbone of the ring.
 11. Thecompound of claim 10, wherein G is nitrogen and R³ forms a methylenebridge to R⁴.
 12. The compound of claim 1, wherein G is nitrogen and ais I and R³ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno and combinations thereof.
 13. Thecompound of claim 1, wherein R³ is benzyl or a substituted orunsubstituted phenyl.
 14. The compound of claim 13, wherein R³ is asubstituted phenyl and there are from 1-5 substituents on said phenylring, with each of said substituents independently selected from thegroup consisting of alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinationsthereof.
 15. The compound of claim 14, wherein there are 1, 2 or 3substituents on said substituted phenyl and said substituents areselected from the group consisting of chloro, fluoro, iodo, bromo,methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl,phenyl, naphthyl, benzyl, trimethylsilyl and isomers thereof.
 16. Thecompound of claim 1, wherein R⁶ is selected from the group consisting ofalkyl, aryl and cycloalkyl and b is 1, 2, 3 or
 4. 17. The compound ofclaim 16, wherein b is 2 and the two R⁶ groups are joined into asubstituted or unsubstituted fused ring structure with the benzene ringin the backbone of the compound.
 18. The compound of claim 1, wherein Gis oxygen and a is
 0. 19. A complex characterized by one of thefollowing general formulas:

wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R⁴ and R⁵ are joined together in aring structure; G is either nitrogen or oxygen and a is 0 or 1 dependingon G; bis 0, 1, 2, 3 or 4; M is a transition metal selected from thegroup consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the PeriodicTable of Elements; L is independently each occurrence, a ligand; n is anumber 0, 1, 2, 3, 4, and 5; and m is 1, 2, 3 or
 4. 20. The complex ofclaim 19, wherein M is selected from the group consisting of Sc, Y, Zr,Ti, Hf, V, Nb, Ta, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt.
 21. Thecomplex of claim 20, wherein M is selected from the group consisting ofPd, Ni, Co, Fe, Ru, Rh, Ir, Pt, Cr, Mo, Mn, and V.
 22. The complex ofclaim 19, wherein L is selected from the group consisting of hydrogen,halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.23. The complex of claim 19, wherein L is selected from the groupconsisting of alkene, diene, carbon monoxide, isocyanide, nitrous oxide,PA₃, NA₃, OA₂, SA₂, SeA₂, and combinations thereof, wherein each A isindependently selected from a group consisting of alkyl, substitutedalkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.24. The complex of claim 19, wherein R¹ is a substituted or unsubstituedphenyl.
 25. The complex of claim 24, wherein R¹ is a substituted phenyland there are from 1-5 substituents on said phenyl ring, with each ofsaid substituents independently selected from the group consisting ofhalogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.26. The complex of claim 25, wherein there are 1, 2 or 3 substituents onsaid substituted phenyl and said substituents are selected from thegroup consisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl,butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 27. The complex of claim 19, whereinR⁴ is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, aryl, substitutearyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino andsilyl.
 28. The complex of claim 27, wherein R⁴ is selected from thegroup consisting of hydrogen, alkyl, aryl and cycloalkyl.
 29. Thecomplex of claim 19, wherein R⁴ is joined in a ring structure with G andR³, wherein said ring has at least four atoms in the backbone of thering.
 30. The complex of claim 29, wherein G is nitrogen and R³ forms amethylene bridge to R⁴.
 31. The complex of claim 19, wherein G isnitrogen and a is 1 and R³ is selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno and combinations thereof.32. The complex of claim 19, wherein R³ is benzyl or a substituted orunsubstituted phenyl.
 33. The complex of claim 32, wherein R³ is asubstituted phenyl and there are from 1-5 substituents on said phenylring, with each of said substituents independently selected from thegroup consisting of halogens, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof.
 34. The complex of claim 33, whereinthere are 1, 2 or 3 substituents on said substituted phenyl and saidsubstituents are selected from the group consisting of chloro, fluoro,iodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl,cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomersthereof.
 35. The complex of claim 19, wherein R⁶ is selected from thegroup consisting of alkyl, aryl and cycloalkyl and b is 1, 2, 3 or 4.36. The complex of claim 19, wherein b is 2 and the two R⁶ groups arejoined into a substituted or unsubstituted fused ring structure with thebenzene ring in the backbone of the compound.
 37. The complex of claim19, wherein G is oxygen and a is
 0. 38. The complex of claim 19, whereineach of R¹ and R² is independently selected from the group consisting ofalkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl andsubstituted aryl.
 39. The complex of claim 19, wherein R¹ and R² arejoined in a ring, wherein the said ring has between 5 and 10non-hydrogen atoms.
 40. The complex of claim 39, wherein said ring hasbetween 5 and 6 non-hydrogen atoms in the backbone of the ring.
 41. Thecomplex of claim 19, wherein each of R¹ and R² is independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, aryl, substitute aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino and silyl.42. The complex of claim 41, wherein each R¹ and R² is independentlyselected from the group consisting of hydrogen alkyl, aryl andcycloalkyl.
 43. A composition of matter comprising the compound of claim1 and a metal precursor characterized by the general formula M(L)_(n),where M is a transition metal selected from the group consisting ofGroups 3, 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements; Lis independently each occurrence, a ligand; and n is a number 0, 1, 2,3, 4, and
 5. 44. The composition of claim 43 wherein the ratio ofcompound to metal precursor is in the range of about 0.01:1 to about100:1.
 45. The composition of claim 44 wherein the ratio of compound tometal precursor is in the range of about 0.5:1 to about 20:1.
 46. Thecomposition of claim 43, wherein the compound is of claim
 5. 47. Thecomposition of claim 43, wherein the compound is of claim
 12. 48. Anarray comprising a plurality of compounds wherein each compound can becharacterized by the general formula:

wherein each R¹, R², R³, R⁴ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof, optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure and/or R⁶ and R¹ are joined in a ring structure; G iseither oxygen or nitrogen and a is 0 or 1 depending on G; and bis 0, 1,2, 3 or
 4. 49. The array of claim 48, wherein each of said plurality ofcompounds has a different composition.
 50. The array of claim 49,wherein each of said plurality of compounds is at a selected region on asubstrate such that each compound is isolated from the other compounds.51. The array of claim 50, wherein said plurality of compounds comprisesat least 10 compounds each having a different composition.
 52. The arrayof claim 50, wherein said plurality of compounds comprises at least 25compounds each having a different composition.
 53. The array of claim50, wherein said plurality of compounds comprises at least 50 compoundseach having a different composition.
 54. The array of claim 48, whereinsaid substrate is a microtiter plate.
 55. The array of claim 50, whereinsaid plurality of compounds are at least 50% pure within said regions.56. A transition metal-catalyzed reaction employing complex in claim 19.57. The reaction of claim 56, wherein the reaction involves C—H, C—C,C—N, C—O, C—S, C—P, C—B and C—Si bond formation.
 58. The reaction ofclaim 57, wherein C—H, C—C, C—N, C—O, C—S, C—P, C—B, and C—Si bondformation involves a sp²-hybridized C atom.
 59. The reaction of claim55, wherein the reactions involve carbonylation, hydroformylation,hydroxycarbonylation, hydrocarbonylation, hydroesterification,hydrogenation, hydrosilylation, hydroboration, hydroamination,epoxidation, aziridation, reductive amination, C—H activation,insertion, C—H activation-insertion, C—H activation-substitution,C-halogen activation, C-halogen activation-substitution, C-halogenactivation-insertion, alkene metathesis, polymerization, alkeneoligomerization, alkene polymerization, alkyne oligomerization, alkynepolymerization, co-polymerization, CO-alkene co-oligomerization,CO-alkene co-polymerization, CO-alkyne co-oligomerization, and CO-alkyneco-polymerization.
 60. A polymerization reaction employing a compoundcharacterized by the general formula:

wherein each R¹, R², R³, R⁴ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure; G is either oxygen or nitrogen and a is 0 or 1 dependingon G; and bis 0, 1, 2, 3 or
 4. 61. The process of claim 60, wherein eachof R¹ and R² is independently selected from the group consisting ofalkyl, substituted alkyl, heteroalkyl, cycloalkyl, substitutedcycloalkyl, aryl and substituted aryl.
 62. The process of claim 60,wherein R¹ and R² are joined in a ring, wherein the said ring hasbetween 5 and 10 non-hydrogen atoms.
 63. The process of claim 62,wherein said ring has between 5 and 6 non-hydrogen atoms in the backboneof the ring.
 64. The process of claim 60, wherein R¹ is a substituted orunsubstitued phenyl.
 65. The process of claim 64, wherein R¹ is asubstituted phenyl and there are from 1-5 substituents on said phenylring, with each of said substituents independently selected from thegroup consisting of halogens, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof.
 66. The process of claim 65, whereinthere are 1, 2 or 3 substituents on said substituted phenyl and saidsubstituents are selected from the group consisting of chloro, fluoro,iodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl,cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomersthereof.
 67. The process of claim 60, wherein R⁴ is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, aryl, substitute aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino and silyl.
 68. Theprocess of claim 67, wherein R⁴ is selected from the group consisting ofhydrogen, alkyl, aryl and cycloalkyl.
 69. The process of claim 60,wherein R⁴ is joined in a ring structure with G and R³, wherein saidring has at least four atoms in the backbone of the ring.
 70. Theprocess of claim 69, wherein G is nitrogen and R³ forms a methylenebridge to R⁴.
 71. The process of claim 60, wherein G is nitrogen and ais 1 and R³ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno and combinations thereof.
 72. The processof claim 71, wherein R³ is benzyl or a substituted or unsubstitutedphenyl.
 73. The process of claim 72, wherein R³ is a substituted phenyland there are from 1-5 substituents on said phenyl ring, with each ofsaid substituents independently selected from the group consisting ofhalogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloallyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.74. The process of claim 73, wherein there are 1, 2 or 3 substituents onsaid substituted phenyl and said substituents are selected from thegroup consisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl,butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 75. A process for polymerizing anolefin, diolefin or acetylenically unsaturated compound, comprisingcontacting said olefin, diolefin or acetylenically unsaturated compoundto a complex that can be characterized by one of the following generalformulas:

wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R⁴ and R⁵ are joined together in aring structure; G is either nitrogen or oxygen and a is 0 or 1 dependingon 0; bis 0, 1, 2, 3 or 4; M is a transition metal selected from thegroup consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the PeriodicTable of Elements; L is independently each occurrence, a ligand; n is anumber 0, 1, 2, 3, 4, and 5; and m is 1, 2, 3 or
 4. 76. The process ofclaim 75, wherein M is selected from the group consisting of Sc, Y, Zr,Ti, Hf, V, Nb, Ta, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt.
 77. Theprocess of claim 76, wherein M is selected from the group consisting ofPd, Ni, Co, Fe, Ru, Rh, Ir, Pt, Cr, Mo, Mn, and V.
 78. The process ofclaim 75, wherein L is selected from the group consisting of hydrogen,halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.79. The process of claim 75, wherein L is selected from the groupconsisting of carbon monoxide, isocyanide, nitrous oxide, PA₃, NA₃, OA₂,SA₂, SeA₂, and combinations thereof, wherein each A is independentlyselected from a group consisting of alkyl, substituted alkyl,heteroalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.
 80. Theprocess of claim 75, wherein R¹ is a substituted or unsubstitued phenyl.81. The process of claim 80, wherein R¹ is a substituted phenyl andthere are from 1-5 substituents on said phenyl ring, with each of saidsubstituents independently selected from the group consisting of alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof.
 82. Theprocess of claim 75, wherein said process is a continuous process at atemperature of between −100° C. and 500° C.
 83. A process for making acompound characterized by the general formula: formula:

wherein each R¹, R², R³, R⁴ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof, optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure; G is either oxygen or nitrogen and a is 0 or 1 dependingon G; and b is 0, 1, 2, 3 or 4; the steps of the process comprising: (1)reacting a compound characterized by the general formula:

where X is selected from the group consisting of chloro, bromo, iodo,triflate and tosylate; and R⁸ and R⁹ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; with an amine characterized by thegeneral formula HNR¹R², where R¹ and R² are as defined above; (2)hydroylzing an acetyl or ketal functionality of the product of thereaction in step (1); and (3) optionally, reacting the product of step(2) with a primary amine.
 84. The process of claim 83, wherein step (1)employs a catalyst that is a composition comprising M′ and L′ where M′ ahomogeneous or heterogeneous metal precursor catalyst or catalyst and L′is a phosphine or nitrogen containing ligand.
 85. The process of claim84, wherein L′ is ligand that is either bidentate, tridentate orhemi-labile and is unsubstituted or substituted, supported orunsupported, water-soluble or insoluble, soluble or insoluble in organicsolvents.
 86. The process of claim 84, wherein M′ includes a metalselected from the group consisting of Pd, Ni or Pt.
 87. The process ofclaim 83, wherein steps (1) and (2) are performed in a one-pot reaction,without the isolation of any product from step (1).
 88. The process ofclaim 83 wherein steps (1), (2) and (3) are performed in a one-potreaction, without the isolation of any product(s) from steps (1) or (2).89. The process of claim 83, wherein step (3) is performed and saidprimary amine may be characterized by the general formula H₂NR³, whereinR³ is as defined above.
 90. The process of claim 89, wherein R³ isbenzyl or a substituted or unsubstituted phenyl.
 91. The process ofclaim 90, wherein R³ is a substituted phenyl and there are from 1-5substituents on said phenyl ring, with each of said substituentsindependently selected from the group consisting of halogens, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof.
 92. Theprocess of claim 91, wherein there are 1, 2 or 3 substituents on saidsubstituted phenyl and said substituents are selected from the groupconsisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl,cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 93. A compound characterized by thegeneral formula:

wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure and/or R⁴ and R⁵ are joined together in a ring structureand/or R⁵ and R⁶ are joined together in a ring structure; G is eitheroxygen or nitrogen and a is either 1 or 2 depending on G; and b is 0, 1,2, 3 or
 4. 94. The compound of claim 93, wherein each of R¹ and R² isindependently selected from the group consisting of alkyl, substitutedalkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl, aryl andsubstituted aryl.
 95. The compound of claim 93, wherein R¹ and R² arejoined in a ring, wherein the said ring has between 5 and 10non-hydrogen atoms.
 96. The compound of claim 95, wherein said ring hasbetween 5 and 6 non-hydrogen atoms in the backbone of the ring.
 97. Thecompound of claim 94, wherein R¹ is a substituted or unsubstituedphenyl.
 98. The compound of claim 97, wherein R¹ is a substituted phenyland there are from 1-5 substituents on said phenyl ring, with each ofsaid substituents independently selected from the group consisting ofhalogens, alky, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.99. The compound of claim 98, wherein there are 1, 2 or 3 substituentson said substituted phenyl and said substituents are selected from thegroup consisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl,butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 100. The compound of claim 93,wherein R⁵ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,aryl, substitute aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, amino and silyl.
 101. The compound of claim 100, wherein R⁵ isselected from the group consisting of hydrogen, alkyl, aryl andcycloalkyl.
 102. The compound of claim 93, wherein R⁴ is selected fromthe group consisting hydrogen, alkoxy, aryloxy, silyl, boryl, phosphino,amino, thio and seleno.
 103. The compound of claim 102, wherein R⁴ is analkoxy.
 104. The compound of claim 93, wherein R⁴ is joined in a ringstructure with G and R³, wherein said ring has at least five atoms inthe backbone of the ring.
 105. The compound of claim 104, wherein G isoxygen and R³ forms a methylene bridge to R⁴ and R⁴ is methoxy.
 106. Thecompound of claim 93, wherein G is nitrogen and a is 2 and the two R³groups are independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno and combinations thereof.107. The compound of claim 93, wherein R⁶ is selected from the groupconsisting of alkyl, aryl and cycloalkyl and b is 1, 2, 3 or
 4. 108. Thecompound of claim 93, wherein b is 2 and the two R⁶ groups are joinedinto a substituted or unsubstituted fused ring structure with thebenzene ring in the backbone of the compound.
 109. A complexcharacterized by one of the following general formulas:

wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R⁴ and R⁵ are joined together in aring structure; G is either nitrogen or oxygen and a is 1 or 2 dependingon G; bis 0, 1, 2, 3 or 4; M is a transition metal selected from thegroup consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the PeriodicTable of Elements; L is independently each occurrence, a ligand; n is anumber 0, 1, 2, 3, 4, and 5; and m is 1, 2, 3 or
 4. 110. The complex ofclaim 109, wherein M is selected from the group consisting of Sc, Y, Zr,Ti, Hf, V, Nb, Ta, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt.
 111. Thecomplex of claim 1 10, wherein M is selected from the group consistingof Pd, Ni, Co, Fe, Ru, Rh, Ir, Pt, Cr, Mo, Mn, and V.
 112. The complexof claim 109, wherein L is selected from the group consisting ofhydrogen, halogens, alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinationsthereof.
 113. The complex of claim 109, wherein L is selected from thegroup consisting of carbon monoxide, isocyanide, nitrous oxide, PA₃,NA₃, OA₂, SA₂, SeA₂, and combinations thereof, wherein each A isindependently selected from a group consisting of alkyl, substitutedalkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.114. The complex of claim 109, wherein R¹ is a substituted orunsubstitued phenyl.
 115. The complex of claim 114, wherein R¹ is asubstituted phenyl and there are from 1-5 substituents on said phenylring, with each of said substituents independently selected from thegroup consisting of halogens, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof.
 116. The complex of claim 115, whereinthere are 1, 2 or 3 substituents on said substituted phenyl and saidsubstituents are selected from the group consisting of chloro, fluoro,iodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl,cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomersthereof.
 117. The complex of claim 109, wherein R⁴ is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, aryl, substitute aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino and silyl.
 118. Thecomplex of claim 117, wherein R⁴ is selected from the group consistingof hydrogen, alkyl, aryl and cycloalkyl.
 119. The complex of claim 109,wherein R⁴ is joined in a ring structure with G and R³, wherein saidring has at least four atoms in the backbone of the ring.
 120. Thecomplex of claim 119, wherein G is nitrogen and R³ forms a methylenebridge to R⁴.
 121. The complex of claim 109, wherein G is nitrogen and ais 2 and each R³ is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno and combinations thereof.122. The complex of claim 109, wherein at least one R³ is benzyl or asubstituted or unsubstituted phenyl.
 123. The complex of claim 122,wherein said R³ is a substituted phenyl and there are from 1-5substituents on said phenyl ring, with each of said substituentsindependently selected from the group consisting of halogens, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof.
 124. Thecomplex of claim 123, wherein there are 1, 2 or 3 substituents on saidsubstituted phenyl and said substituents are selected from the groupconsisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl,cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 125. The complex of claim 109,wherein R⁶ is selected from the group consisting of alkyl, aryl andcycloalkyl and b is 1, 2, 3 or
 4. 126. The complex of claim 109, whereinb is 2 and the two R⁶ groups are joined into a substituted orunsubstituted fused ring structure with the benzene ring in the backboneof the compound.
 127. The complex of claim 109, wherein G is oxygen anda is
 1. 128. The complex of claim 109, wherein R¹ and R² are joined in aring, wherein the said ring has between 5 and 10 non-hydrogen atoms.129. The complex of claim 129, wherein said ring has between 5 and 6non-hydrogen atoms in the backbone of the ring.
 130. The complex ofclaim 109, wherein each of R¹ and R² is independently selected from thegroup consisting of alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heteroalkyl, aryl, substitute aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino and silyl.
 131. The complex of claim109, wherein R⁵ is selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, aryl, substitute aryl, heteroaryl, substituted heteroaryl,alkoxy, aryloxy, amino and silyl.
 132. The complex of claim 131, whereinR⁵ is selected from the group consisting of hydrogen, alkyl, aryl andcycloalkyl.
 133. A composition of matter comprising the compound ofclaim 93 and a metal precursor characterized by the general formulaM(L)_(n), where M is a transition metal selected from the groupconsisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table ofElements; L is independently each occurrence, a ligand; and n is anumber 0, 1, 2, 3, 4, and
 5. 134. The composition of claim 133 whereinthe ratio of compound to metal precursor is in the range of about 0.01:1to about 100:1.
 135. The composition of claim 134 wherein the ratio ofcompound to metal precursor is in the range of about 0.5:1 to about20:1.
 136. The composition of claim 133, wherein the compound is ofclaim
 97. 137. The composition of claim 133, wherein the compound is ofclaim
 106. 138. An array comprising a plurality of compounds whereineach compound can be characterized by the general formula:

wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure; G is either oxygen or nitrogen and a is either I or 2depending on G; and bis 0, 1, 2, 3 or
 4. 139. The array of claim 138,wherein each of said plurality of compounds has a different composition.140. The array of claim 139, wherein each of said plurality of compoundsis at a selected region on a substrate such that each compound isisolated from the other compounds.
 141. The array of claim 140, whereinsaid plurality of compounds comprises at least 10 compounds each havinga different composition.
 142. The array of claim 140, wherein saidplurality of compounds comprises at least 25 compounds each having adifferent composition.
 143. The array of claim 140, wherein saidplurality of compounds comprises at least 50 compounds each having adifferent composition.
 144. The array of claim 140, wherein saidsubstrate is a microtiter plate.
 145. The array of claim 140, whereinsaid plurality of compounds are a t least 50% pure within said regions.146. A transition metal-catalyzed reaction employing complex in claim109.
 147. The reaction of claim 146, wherein the reaction involves C—H,C—C, C—N, C—O, C—S, C—P, C—B and C—Si bond formation.
 148. The reactionof claim 146, wherein C—H, C—C, C—N, C—O, C—S, C—P, C—B, and C—Si bondformation involves a sp²-hybridized C atom.
 149. The reaction of claim146, wherein the reactions involve carbonylation, 5 hydroformylation,hydroxycarbonylation, hydrocarbonylation, hydroesterification,hydrogenation, hydrosilylation, hydroboration, hydroamination,epoxidation, aziridation, reductive amination, C—H activation,insertion, C—H activation-insertion, C—H activation-substitution,C-halogen activation, C-halogen activation-substitution, C-halogenactivation-insertion, alkene metathesis, polymerization, alkeneoligomerization, alkene polymerization, alkyne oligomerization, alkynepolymerization, co-polymerization, CO-alkene co-oligomerization,CO-alkene co-polymerization, CO-alkyne co-oligomerization, and CO-alkyneco-polymerization.
 150. A polymerization reaction employing a compoundcharacterized by the general formula:

wherein each R¹, R², R³, R⁴, R⁵ and R⁶ is independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, 20 heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure and/or R⁴ and R⁵ -are joined together in a ring structureand/or R¹ and R⁶ are joined together in a ring structure; G is eitheroxygen or nitrogen and a is 1 or 2 depending on G; and bis 0, 1, 2, 3 or4.
 151. The process of claim 150, wherein each of R¹ and R² isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl, aryland substituted aryl.
 152. The process of claim 150, wherein R¹ and R²are joined in a ring, wherein the said ring has between 5 and 10non-hydrogen atoms.
 153. The process of claim 152, wherein said ring hasbetween 5 and 6 non-hydrogen atoms in the backbone of the ring.
 154. Theprocess of claim 150, wherein R¹ is a substituted or unsubstituedphenyl.
 155. The process of claim 154, wherein R¹ is a substitutedphenyl and there are from 1-5 substituents on said phenyl ring, witheach of said substituents independently selected from the groupconsisting of halogens, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof.
 156. The process of claim 155, whereinthere are 1, 2 or 3 substituents on said substituted phenyl and saidsubstituents are selected from the group consisting of chloro, fluoro,iodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl,cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomersthereof.
 157. The process of claim 150, wherein R⁴ is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, aryl, substitute aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino and silyl.
 158. Theprocess of claim 157, wherein R⁴ is selected from the group consistingof hydrogen, alkyl, aryl and cycloalkyl.
 159. The process of claim 150,wherein R⁴ is joined in a ring structure with G and R³, wherein saidring has at least four atoms in the backbone of the ring.
 160. Theprocess of claim 159, wherein G is nitrogen and R³ forms a methylenebridge to R⁴.
 161. The process of claim 150, wherein G is nitrogen and ais 2 and each R³ is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno and combinations thereof.162. The process of claim 161, wherein at least one R³ is benzyl or asubstituted or unsubstituted phenyl.
 163. The process of claim 162,wherein said R³ is a substituted phenyl and there are from 1-5substituents on said phenyl ring, with each of said substituentsindependently selected from the group consisting of halogens, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof.
 164. Theprocess of claim 163, wherein there are 1, 2 or 3 substituents on saidsubstituted phenyl and said substituents are selected from the groupconsisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl,cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 165. The process of claim 150,wherein R⁵ is selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, aryl, substitutearyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino andsilyl.
 166. The process of claim 165, wherein R⁵ is selected from thegroup consisting of alkyl, aryl and cycloalkyl.
 167. A process forpolymerizing an olefin, diolefin or acetylenically unsaturated compound,comprising contacting said olefin, diolefin or acetylenicallyunsaturated compound to a complex that can be characterized by one ofthe following general formulas:

wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R⁴ and R⁵ are joined together in aring structure and/or R⁴ and R⁵ are joined together in a ring structureand/or R⁵ and R⁶ are joined together in a ring structure; G is eithernitrogen or oxygen and a is 1 or 2 depending on G; bis 0, 1, 2, 3 or 4;M is a transition metal selected from the group consisting of Groups 3,4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements; L isindependently each occurrence, a ligand; n is a number 0, 1, 2, 3, 4,and 5; and m is 1, 2, 3 or
 4. 168. The process of claim 167, wherein Mis selected from the group consisting of Sc, Y, Zr, Ti, Hf, V, Nb, Ta,Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt.
 169. The process of claim 168,wherein M is selected from the group consisting of Pd, Ni, Co, Fe, Ru,Rh, Ir, Pt, Cr, Mo, Mn, and V.
 170. The process of claim 167, wherein Lis selected from the group consisting of hydrogen, halogens, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof.
 171. Theprocess of claim 167, wherein L is selected from the group consisting ofcarbon monoxide, isocyanide, nitrous oxide, PA₃, NA₃, OA₂, SA₂, SeA₂,and combinations thereof, wherein each A is independently selected froma group consisting of alkyl, substituted alkyl, heteroalkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, and amino.
 172. The process of claim 167, wherein R¹ isa substituted or unsubstitued phenyl.
 173. The process of claim 172,wherein R¹ is a substituted phenyl and there are from 1-5 substituentson said phenyl ring, with each of said substituents independentlyselected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino,thio, seleno, and combinations thereof.
 174. The process of claim 167,wherein said process is a continuous process run at a temperature ofbetween −100° C. and 500° C.
 175. A process for making a compoundcharacterized by the general formula: formula:

wherein each R¹, R², R³, R⁴ R⁵ and R⁶ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; optionally, R¹ and R² are joinedtogether in a ring structure and/or R³ and R⁴ are joined together in aring structure; G is either oxygen or nitrogen and a is 1 or 2 dependingon G; and bis 0, 1, 2, 3 or 4; the step of the process comprising: (1)reacting a compound characterized by the general formula:

where X is selected from the group consisting of chloro, bromo, iodo,triflate and tosylate; and R⁸ and R⁹ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof; with an amine characterized by thegeneral formula HNR¹R², where R¹ and R² are as defined above.
 176. Theprocess of claim 175, wherein step (1) employs a catalyst that is acomposition comprising M′ and L′ where M′ a homogeneous or heterogeneousmetal precursor catalyst or catalyst and L′ is a phosphine or nitrogencontaining ligand.
 177. The process of claim 176, wherein L′ is ligandthat is either bidentate, tridentate or hemi-labile and is unsubstitutedor substituted, supported or unsupported, water-soluble or insoluble,soluble or insoluble in organic solvents.
 178. The process of claim 176,wherein M′ includes a metal selected from the group consisting of Pd, Nior Pt.
 179. The process of claim 175, further comprising the steps of:(2) hydroylzing an acetyl or ketal functionality of the product of thereaction in step (1); and (3) reacting the product of step (2) with anamine;
 180. The process of claim 179, wherein steps (1) and (2) areperformed in a one-pot reaction, without the isolation of any productfrom step (1).
 181. The process of claim 179 wherein steps (1), (2) and(3) are performed in a one-pot reaction, without the isolation of anyproduct(s) from steps (1) or (2).
 182. The process of claim 179, whereinsaid amine in step (3) is a primary amine which may be characterized bythe general formula H₂NR³, wherein R³ is as defined above.
 183. Theprocess of claim 179, wherein R³ is benzyl or a substituted orunsubstituted phenyl.
 184. The process of claim 183, wherein R³ is asubstituted phenyl and there are from 1-5 substituents on said phenylring, with each of said substituents independently selected from thegroup consisting of halogens, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, and combinations thereof.
 185. The process of claim 184, whereinthere are 1, 2 or 3 substituents on said substituted phenyl and saidsubstituents are selected from the group consisting of chloro, fluoro,iodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl,cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomersthereof.
 186. The process of claim 179, wherein said amine in step (3)is a secondary amine which may be characterized by the general formulaHNR³ ₂, wherein each R³ is as defined above.
 187. The process of claim186, wherein each R³ is independently selected from the group consistingof benzyl or a substituted or unsubstituted phenyl.
 188. The process ofclaim 187, wherein R3 is a substituted phenyl and there are from 1-5substituents on said phenyl ring, with each of said substituentsindependently selected from the group consisting of halogens, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl,phosphino, amino, thio, seleno, and combinations thereof.
 189. Theprocess of claim 188, wherein there are 1, 2 or 3 substituents on saidsubstituted phenyl and said substituents are selected from the groupconsisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl,cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl,trimethylsilyl and isomers thereof.
 190. The process of claim 179,further comprising step (4) wherein said step is a hydrogenationreaction of the product of step (3).